Material for solar benches

ABSTRACT

The invention describes a polymer with high transmission for UV rays, this transmission being preserved even after prolonged exposure to UV light (tanning lamps). The polymer is further characterized by a low residual monomer content (determined as methyl methacrylate).

FIELD OF THE INVENTION

[0001] The present invention relates to an improved material for covering the UV lamps in tanning beds.

PRIOR ART

[0002] From European Patent 0016870 there are already known plastics based on methyl methacrylate which have high transmission for UV A radiation (315 to 380 nm) and for UV B radiation (280 to 315 nm). Their high UV transmission is preserved even during prolonged exposure to radiation if the plastic contains a small concentration of a sterically hindered amine. Corresponding compounds trap radicals which are formed during radiation exposure and which would otherwise slowly destroy the plastic material. Such additives are described in Japanese Patent 03-47856, and are known as “hindered amine light stabilizers” or HALS. Plastics which are based on polymethyl methacrylate (PMMA), which contain sterically hindered amines and which have high UV transmission are also described in German Unexamined Specification DE-OS 3421859. Heretofore Plexiglas® GS 2458 (commercial product of Rohm GmbH) has been used to cover the UV lamps of tanning beds. The material is easy to care for and transmits a high percentage of tanning UV radiation. The thickness of the covers used has ranged between 3 and 8 mm.

[0003] Since both the radiant power of UV lamps on the whole and the UVB component of the radiation have increased in the course of technical development, a considerable reduction of transmission is suffered in standard materials with thicknesses of >4 mm after about 20 hours of exposure.

[0004] Exposure results

[0005] In this case: standard formula (Plexiglas® 2458), 8 mm thick, tempered (30 minutes, 160° C.). Lamp: light box, Ergoline ST Turbo Power lamps, 9 tubes: Irradiation time (h) 0 50 125 275 475 Transmission at 315 nm in % 80 60 45 33 25

[0006] A yellow discoloration known as yellow core develops in the interior of the plate. The UV light is absorbed, the customer no longer becomes tanned and the plate must be replaced relatively early.

[0007] Object

[0008] The object was therefore to provide a material which, even at the lamp intensities that are common today, yellows not at all or only slightly while also having high UV transmission. At the same time, it must be ensured that the additives which prevent development of the yellow core are physiologically safe. Only substances which are approved by the FDA and are in conformity with the European Union and German Health Agency directives may be added. It is intended that plates will be made available which do not exhibit yellow core even at the lamp powers which are standard today in combination with material thicknesses of more than 4 mm. The large thicknesses of more than 4 mm are necessary, since the cover of the UV lamps has cantilever structure and the plates are hot-formed at about 160° C.

[0009] Achievement

[0010] Good UV transmission over a long period is a primary requirement for tanning bed material.

[0011] It has now been found that the object can be achieved by addition of alcohols, alcohol mixtures and even water and/or further compounds to the monomer mixture of the standard formula. The compound or the mixture respectively being used will be referred to hereinafter as active components. Examples of suitable alcohols are monohydric or polyhydric C1 to C10 alcohols, which may also be branched, such as methanol, ethanol, propanol, isopropanol or tert-butanol or pentanols. A further improvement can be achieved by the use of further compounds, such as vinyl compounds, butyl lactate and siloxanes as well as mixtures of the said compounds. Vinyl compounds can be understood as vinyl esters of aliphatic carboxylic acids, such as vinyl acetate. There can also be used vinyl esters of general formula I:

[see original for formula] (Formula I)

[0012] where: R₁, R₂ and R₃ are alkyl groups, wherein at least one group represents a methyl group. The total number of carbon atoms in groups R₁ to R₃ is 9, 10 or 11.

[0013] The compounds of formula I are available from Shell Chemicals under the names VeoVa9 (9 carbon atoms, R₁ to R₃), VeoVa10 (10 carbon atoms, R₁ to R₃) or VeoVa11 (11 carbon atoms, R₁ to R₃).

[0014] The alcohols, alcohol mixtures or further active components are mixed in with the monomer mixture in proportions of 0.1 to 10 wt %. Contents of 0.2 to 8 wt % of active components are preferred, and contents of 0.2 to 6 wt % of active components are especially preferred.

[0015] Methyl methacrylate comprises 85 to 95 wt % of the monomer mixture.

[0016] Composition of the standard formula: 93.85 wt % Methyl methacrylate 6% Acetyl tributyl citrate (as plasticizer) Citrofol B2 (Jungbunzlauer Co.) 0.1 wt % Tinuvin 770 (Ciba) (HALS) 0.05 wt % Initiator

[0017] As initiator there can be used the initiators that are standard in cast polymerization; see H. Rauch-Puntigam, Th. Volker in “Acrylic and Methacrylic Compounds”, Springer-Verlag 1967; Houben-Weyl, 4th Edition, Volume XIV/1, Macromolecular Substances, Part 1, pp. 1010 to 1078, Georg Thieme Verlag, 1961).

[0018] As plasticizer there can be used acetyl tributyl citrate or triethyl citrate. In some cases it may also be possible to omit the plasticizer.

EXAMPLES

[0019] General Manufacturing Procedure

[0020] The standard formula and the mixtures of active compounds are intimately mixed, filled into glass chambers sealed with PVC shaped cord and polymerized in the water bath under the following temperature and time conditions: Duration (h) 6-7 15  4 Temperature (° C.) 46 40 100

[0021] After the first polymerization step, the shaped cord is removed. After the 2nd polymerization step, final polymerization takes place at elevated temperature. If necessary, further tempering at elevated temperature (160° C.) can be performed.

[0022] The resulting PMMA plate is cut to size (100×30×8 mm) and exposed. Exposure of the specimens was accomplished using Philips UVA+UVB Performance individual lamps or Ergoline Turbo Power individual lamps or on an Ergoline light box with 9 Ergoline Turbo Power lamps.

[0023] The Ergoline SR Turbo Power lamp (manufactured by IK Licht GmbH, Item No. 1085518) has an electrical power of 160 W and a UVA radiant flux of 38 watt.

EXAMPLES Example 1 Standard Formula

[0024] Time (h) 0 67 115 223 731 Transmission tau (315 nm) 80 53 46 33 17

[0025] Exposure is performed on Ergoline SR Turbo Power

Example 2

[0026] Composition Standard +

[0027] 0.095 wt % of methanol

[0028] 0.95 wt % of ethanol

[0029] 0.95 wt % of isopropanol

[0030] 0.5 wt % of H₂O

[0031] The MMA content of the standard formula was correspondingly reduced. Time (h) 0 5 117 213 577 Transmission tau (315 nm) 81 75 83 85 87

[0032] Exposure is performed on Ergoline SR Turbo Power

[0033] The percentages plus standard add up to 100%, the content of methyl methacrylate being reduced by an amount corresponding to the content of active compounds.

Example 3

[0034] Composition Standard +

[0035] 0.095 wt % of methanol

[0036] 0.95 wt % of ethanol

[0037] 0.95 wt % of isopropanol

[0038] 0.5 wt % of butyl lactate Time (h) 0 20 133 329 464 Transmission tau (315 nm) 83 70 85 87 88

[0039] Exposure is performed in the Ergoline SR Turbo Power light box

[0040] As a further positive effect of the alcohol addition, it was surprisingly found that the content of residual monomers, measured as methyl methacrylate, decreases from the usual 0.3 to 0.4 wt % to 0.2 wt %.

[0041] A particularly large decrease of residual monomer content is found when alcohol and vinyl acetate are used. In this case the residual monomer content decreases to 0.019 wt %.

[0042] Residual Monomer Contents Example Wt % (as methyl methacrylate) 1 0.41 2 0.22 3 0.19 4 0.019 5 not determined 6 0.067 7 0.031

[0043] The residual monomer contents were determined by vapor space gas chromatography.

Example 4

[0044] Standard +

[0045] 0.5 wt % of H₂O

[0046] 0.95 wt. % of ethanol

[0047] 0.5 wt. % of vinyl acetate Time (h) 0 96 252 384 1636 Transmission tau (315 nm) 82 72 81 84 86

[0048] Exposure is performed in the Ergoline SR Turbo Power light box

Example 5

[0049] Standard +

[0050] 0.095 wt % of methanol

[0051] 0.95 wt % of isopropanol

[0052] 1.0 wt % of vinyl acetate Time (h) 0 16 196 475 Transmission tau (315 nm) 82 76 83 87

[0053] Exposure is performed in the Ergoline SR Turbo Power light box

Example 6

[0054] Standard +

[0055] 0.095 wt % of methanol

[0056] 1.0 wt % of VEOVA 10

[0057] 0.95 wt % of ethanol Time (h) 0 20 63 150 500 Transmission tau (315 nm) 83 71 76 81 87

[0058] Exposure is performed in the Ergoline SR Turbo Power light box Time (h) 1000 1500 2000 Transmission tau (315 nm) 89 90 90

[0059] Exposure is performed in the Ergoline SR Turbo Power light box

Example 7

[0060] Formula according to Example 6, but with 3 wt % of VEOVA10 and 3% of Citrofol B2 Time (h) 0 20 150 200 315 1000 2000 Transmission tau (315 nm) 83 75 77 77 79 85 87

[0061] Exposure is performed in the Ergoline SR Turbo Power light box

Example 8

[0062] Standard formula +

[0063] 0.095 wt % of methanol

[0064] 0.95 wt % of ethanol

[0065] 1.0 wt % of butyl lactate Time (h) 0 40 128 380 783 Transmission tau (315 nm) 83 75 85 87 88

[0066] Exposure is performed in the Ergoline SR Turbo Power light box

[0067] Even after exposures of >1000 hours, the transmission of the inventive plates does not decrease in any of the examples (except for Example 1, “standard”).

Example 9

[0068] Standard formula +

[0069] 1.0% of methanol Time (h) 500 1000 2000 Transmission tau (315 nm) 76 88 85

[0070] Exposure is performed in the Ergoline SR Turbo Power light box

Example 10

[0071] Standard formula +

[0072] 0.8% of methanol

[0073] 0.5% of water Time (h) 500 1000 2000 3000 Transmission tau (315 nm) 73 80 84 84

[0074] Exposure is performed in the Ergoline SR Turbo Power light box

Example 11

[0075] Standard formula +

[0076] 0.2% of water

[0077] 0.8% of methanol Time (h) 0 67 100 250 500 700 Transmission tau (315 nm) 87 82 76 82 85 85

[0078] Philips UVB Performance

Example 12

[0079] Standard formula +

[0080] 0.5% of water

[0081] 0.5% of methanol Time (h) 112 206 275 Transmission tau (315 nm) 88 89 89

[0082] Exposure is performed with Ergoline SR Turbo Power.

[0083] Before exposure, the plate of Example 12 was tempered for 30 minutes at 160° C. Exposure was performed by individual lamps. 

1. PMMA materials, which can be made by radical polymerization of the following monomer mixture: 88 to 95 wt % of methyl methacrylate 0 to 7% of plasticizer 0.01 to 0.5 wt % of HALS compound 0.05 wt % of initiator and 0.1 to 10 wt % of an active component


2. PMMA materials according to claim 1, characterized in that alcohols, water or vinyl compounds or butyl lactate are used individually or in mixtures as active components.
 3. PMMA materials according to claim 1, characterized in that methanol, ethanol or propanol or isopropanol or n-butanol, sec-butanol, tert-butanol or pentanols are used individually or in mixtures as alcohols.
 4. PMMA materials according to claim 1, characterized in that as vinyl compounds there are used vinyl acetate or compounds of formula I [see original for formula] (Formula I) where R₁, R₂ and R₃ are alkyl groups, wherein at least one group represents a methyl group, the total number of carbon atoms in groups R₁ to R₃ being 9, 10 or
 11. 5. The use of the materials according to one of the preceding claims for covering the lamps in tanning beds.
 6. The use of the materials according to one of the preceding claims as glazing material. 